Polymerization in monolayers

In tbe first attempt to prepare a two-dimensional crystalline polymer (45), Co y-radiation was used to initiate polymerization in monolayers of vinyl stearate (7). Polymerization at the air—water interface was possible but gave a rigid film. The monomeric monolayer was deposited to give X-type layers that could be polymerized in situ This polymerization reaction, quenched by oxygen, proceeds via a free-radical mechanism. 

The same authors also detected that polymerization in monolayers is strongly affected by oxygen. They assumed that the conjugated polymer chains are affected by ozon, which is simultaneously formed by the intense UV-irradiation of the sample. 

Chemical properties of deposited monolayers have been studied in various ways. The degree of ionization of a substituted coumarin film deposited on quartz was determined as a function of the pH of a solution in contact with the film, from which comparison with Gouy-Chapman theory (see Section V-2) could be made [151]. Several studies have been made of the UV-induced polymerization of monolayers (as well as of multilayers) of diacetylene amphiphiles (see Refs. 168, 169). Excitation energy transfer has been observed in a mixed monolayer of donor and acceptor molecules in stearic acid [170]. Electrical properties have been of interest, particularly the possibility that a suitably asymmetric film might be a unidirectional conductor, that is, a rectifier (see Refs. 171, 172). Optical properties of interest include the ability to make planar optical waveguides of thick LB films [173, 174]. 

Biddle M B, Lando J B, Ringsdorf H, Schmidt G and Schneider J 1988 Polymeric amphiphiles with hydrophilic main chain spacers—studies in monolayers and Langmuir-Blodgett multilayers Oollold Polymer Scl. 266 806-13... 

High quahty SAMs of alkyltrichlorosilane derivatives are not simple to produce, mainly because of the need to carefully control the amount of water in solution (126,143,144). Whereas incomplete monolayers are formed in the absence of water (127,128), excess water results in facile polymerization in solution and polysiloxane deposition of the surface (133). Extraction of surface moisture, followed by OTS hydrolysis and subsequent surface adsorption, may be the mechanism of SAM formation (145). A moisture quantity of 0.15 mg/100 mL solvent has been suggested as the optimum condition for the formation of closely packed monolayers. X-ray photoelectron spectroscopy (xps) studies confirm the complete surface reaction of the —SiCl groups, upon the formation of a complete SAM (146). Infrared spectroscopy has been used to provide direct evidence for the hiU hydrolysis of methylchlorosilanes to methylsdanoles at the soHd/gas interface, by surface water on a hydrated siUca (147). 

Patterns of ordered molecular islands surrounded by disordered molecules are common in Langmuir layers, where even in zero surface pressure molecules self-organize at the air—water interface. The difference between the two systems is that in SAMs of trichlorosilanes the island is comprised of polymerized surfactants, and therefore the mobihty of individual molecules is restricted. This lack of mobihty is probably the principal reason why SAMs of alkyltrichlorosilanes are less ordered than, for example, fatty acids on AgO, or thiols on gold. The coupling of polymerization and surface anchoring is a primary source of the reproducibihty problems. Small differences in water content and in surface Si—OH group concentration may result in a significant difference in monolayer quahty. Alkyl silanes remain, however, ideal materials for surface modification and functionalization apphcations, eg, as adhesion promoters (166—168) and boundary lubricants (169—171). 

In order to investigate the phase transition in the monolayer state, the temperature dependence of the Jt-A isotherm was measured at pH 2. The molecular area at 20 mN rn 1, which is the pressure for the LB transfer of the polymerized monolayer, is plotted as a function of temperature (Figure 2.6). Thermal expansion obviously changes at around 45 °C, indicating that the polymerized monolayer forms a disordered phase above this temperature. The observed temperature (45 °C) can be regarded as the phase transition point from the crystalline phase to the liquid crystalline phase of the polymerized organosilane monolayer. 

Compression- and Shear-Induced Polymerization in Model Diacetylene-Containing Monolayers. 

On the contrary, butadiene and methacryloyl monomers (1,3,4, 10,11) can also be polymerized in the liquid expanded phase. The butadiene lipids have previously been shown to form 1,4-trans-poly(butadiene)s (40j in the monolayer (Eqn. II.). 

Polymerization in Bilayers. Upon irradiation with UV light the monomer vesicles are transferred to polymer vesicles (Figure 12.). In the case of the diyne monomers (2,5-9,12,13,14) the polyreaction can again be followed by the color change via blue to red except phospholipids (5,6), which turn red without going through the blue intermediate as observed in monolayers. The VIS spectra of these polymer vesicle dispersions are qualitatively identical to those of the polymer monolayers (Figure 13.). 

Polymerization in microemulsions allows the synthesis of ultrafine latex particles in the size range of 5 to 50 nm with a narrow size distribution [33], The deposition of an ordered monolayer of such spheres is known to be increasingly difficult as the diameter of such particles decreases [34], Vigorous Brownian motion and capillary effects create a state of disorder in the system that is difficult... 

LB films have also been prepared from simple (20, for example) [165] and functionalized (21, for example) [166] amphiphatic diacetylenes. Two different approaches were pursued. In the first approach, diacetylenes were polymerized as monolayers and subsequently transferred to substrates to generate LB films. In the second approach, LB films were formed from monomeric diacetylenes and were subsequently polymerized. Strong absorption of polydiacetylenes in... 

Diacetylene monolayer photopolymerization was found to be topochemical it only occurred in the two-dimensional solid state of the surfactants. Polymerized diacetylenes, both in monolayers and in LB films, were found to be rather rigid and prone to cracking [160]. This undesirable property somewhat limits the exploitation of polymerized diacetylene LB films for potential electronic applications. 

In choosing a SAM system for surface engineering, there are several options. Silane monolayers on hydroxylated surfaces are an option where transparent or nonconductive systems are needed. However, trichlorosilane compounds are moisture-sensitive and polymerize in solution. The resulting polymers contaminate the monolayer surface, which occasionally has to be cleaned mechanically. Carboxylic acids adsorb on metal oxide, eg, A1 03, AgO through acid—base interactions. These are not specific therefore, it would be impossible to adsorb a carboxylic acid selectively in the presence of, for example, a terminal phosphonic acid group. In many studies SAMs of thiolates on Au(lll) are the system of choice. 

The complexity and the lack of commercial pure standards of PA make their analysis difficult. Their absorption depends on their degree of polymerization. In some in vitro experiments, only PA dimers and trimers, but not polymers with an average polymerization degree of 7, were absorbed through an intestinal epithelium cell monolayer [118]. Experiments in chicken and sheep showed that polymeric PAs were not absorbed through gut barrier [119,120]. 

Besides polymerization, another type of polyreaction can be used for stabilizing model membrane systems. Recently, Fukuda et al.28) described polyamide formation via polycondensation in monolayers at the gas/water interface (definition of mono-layers see Sect. 3.2). Long-chain esters of glycine and alanine were polycondensed to yield non-oriented polyamide films of polyglycine and polyalanine. 

Besides the polymerization of diacetylenes, butadienes and acrylates, the polycondensation behavior of long-chain ot-amino acids, diamines and diesters has been investigated in monolayers 52. ... 

Aqueous dispersions of polymerizable lipids and surfactants can be polymerized by UV irradiation (Fig. 18). In the case of diacetylenic lipids the transition from monomeric to polymeric bilayers can be observed visually and spectroscopically. This was first discussed by Hub, 9) and Chapman 20). As in monomolecular layers (3.2.2) short irradiation brings about the blue conformation of the poly(diacetylene) chain. In contrast, upon prolonged irradiation or upon heating blue vesicles above the phase transition temperature of the monomeric hydrated lipid the red form of the polymer is formed 23,120). The visible spectra of the red form in monolayers and liposomes are qualitatively identical (Fig. 19). 

Polycondensation reactions in oriented monolayers and bilayers proceed without catalysis, and simply occur due to the high packing density of the reactive groups and their orientation in these layers. Bulk condensation of the a-amino acid esters at higher temperatures does not lead to polypeptides but to 2,5-diketopiperazines. No diketopiperazines are found in polycondensed monolayers or liposomes. Polycondensation in monolayers and liposomes leading to oriented polyamides represents a new route for stabilizing model membranes under mild conditions. In addition, polypeptide vesicles may be cleavable by enzymes in the blood vessels. In this case, they would represent the first example of stable but biodegradable polymeric liposomes. 

Their phase and polymerization behavior were characterized in monolayers and vesicles 62). 

Surface pressure/area isotherms of mixtures of the cationic lipid (20, n = 12) with distearoylphosphatidylcholine (DSPC) are shown in Fig. 30. For all mixtures only one collapse point is observed. The collapse pressure increases continuously with increasing amount of DSPC, indicating miscibility of the two components. Plotting A versus molar ratio (Fie. 3D results in considerable deviation from linearity, which also suggests miscibility of the two compounds in monolayers. This is also confirmed by the fact that the polymerization rate, as measured by the increase of optical density at 540 nm, is reduced by a factor of 100 when the DSPC molar ratio is increased from 0 to 0.52,... 

Herbicides, like demestryn, have been determined using a chemosensor based on the MIP film recognition and capacitive transduction [193, 194]. In this determination, photografting polymerization has been demonstrated as an efficient procedure for fabrication of a capacitive chemosensor. This procedure involved immobilization of an initiator on the electrode. In this case, first, an alkanethiol monolayer was self-assembled on the gold electrode. This monolayer was perfectly dielectric. Then, an MIP film was deposited on top of this monolayer by photo-radical polymerization in the acetone solution with benzophenone, 2-acrylamido-2-methyl-1-propane sulphonic acid, /V./V -iriethylenediacrylamide and demestryn used as the initiator, cross-linker, functional monomer and template, respectively. Subsequently, the template was extracted with methanol. The capacitance decreased by 20% upon binding the demestryn analyte by the MIP film. Similarly, a creatine chemosensor was constructed [194],... 

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